This application claims priority under 35 U.S.C. xc2xa7119 of FR-01/15859, filed Dec. 7, 2001, hereby expressly incorporated by reference.
1. Technical Field of the Invention
The invention relates to a cosmetic or dermatological composition for topical use, in particular for the photoprotection of the skin and hair, characterized in that it comprises, in a cosmetically acceptable vehicle:
(a) at least one dibenzoylmethane derivative and
(b) at least one 1,3,5-triazine derivative which is photosensitive in the presence of a dibenzoylmethane derivative and
(c) at least one specific amino-substituted 2-hydroxy-benzophenone derivative; the said composition not comprising p-methyl-benzylidenecamphor.
The invention also relates to a process for improving the photostability of a 1,3,5-triazine derivative which is photosensitive in the presence of a UV screening agent of the dibenzoylmethane derivative type, which process consists in adding, to the triazine derivative/dibenzoylmethane derivative combination, an effective amount of at least one specific amino-substituted 2-hydroxybenzophenone derivative.
2. Description of the Prior Art
It is known that light radiation with wavelengths of between 280 nm and 400 nm makes possible browning of the human epidermis and that rays with wavelengths more particularly of between 280 and 320 nm, known under the name of UV-B, cause erythemas and skin burns which may be harmful to the development of natural tanning. For these reasons, as well as for aesthetic reasons, there is a constant demand for means for controlling this natural tanning for the purpose of thus controlling the color of the skin; it is therefore advisable to screen out this UV-B radiation.
It is also known that UV-A rays, with wavelengths of between 320 and 400 nm, which cause browning of the skin, are capable of bringing about a detrimental change in the latter, in particular in the case of sensitive skin or of skin continually exposed to solar radiation. UV-A rays cause in particular a loss in the elasticity of the skin and the appearance of wrinkles, resulting in premature aging of the skin. They promote the triggering of the erythemal reaction or accentuate this reaction in some subjects and can even be the cause of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons, such as the preservation of the natural elasticity of the skin, for example, more and more people wish to control the effect of UV-A rays on the skin. It is therefore desirable also to screen out UV-A radiation.
In this respect, a particularly advantageous family of UV-A screening agents currently consists of dibenzoylmethane derivatives and in particular 4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane, as they exhibit a high intrinsic absorbance. These dibenzoylmethane derivatives, which are now products well known per se as screening agents active in the UV-A region, are disclosed in particular in French Patent Applications FR-A-2,326,405 and FR-A-2,440,933 and in European Patent Application EP-A-0,114,607; furthermore, 4-tert-5 butyl-4xe2x80x2-methoxydibenzoylmethane is currently offered for sale under the trademark xe2x80x9cParsol 1789xe2x80x9d by Hoffmann-LaRoche.
1,3,5-Triazine derivatives are particularly sought for in antisun cosmetics because they are highly active in the UV-B region and even in the UV-A region for some of these compounds, depending on the nature of the substituents involved. They are disclosed in particular in U.S. Pat. No. 4,367,390, EP-863,145, EP-517,104, EP-570,838, EP-507,691, EP-796,851, EP-775,698, EP-878,469 and EP-933,376, and the following are known in particular:
2,4,6-tris[p-(2xe2x80x2-ethylhexyl-1xe2x80x2-oxycarbonyl)-anilino]-1,3,5-triazine or xe2x80x9cEthylhexyl Triazonexe2x80x9d (INCI name), sold under the trademark xe2x80x9cUvinul T 150xe2x80x9d by BASF,
2-[p-(tert-butylamido)anilino]-4,6-bis[p-(2xe2x80x2-ethylhexyl-1xe2x80x2-oxycarbonyl)anilino]-1,3,5-triazine or xe2x80x9cDiethylhexyl Butamido Triazonexe2x80x9d (INCI name), sold under the trademark xe2x80x9cUvasorb HEBxe2x80x9d by Sigma 3V. They have a high absorbance for UV-B radiation and it would therefore be highly advantageous to be able to use them in combination with the abovementioned 4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane with the aim of obtaining products offering broad and effective protection in the entire UV radiation region.
Antisun compositions formed from amino-substituted 2-hydroxybenzophenone derivatives which can comprise other additional screening agents, such as dibenzoylmethane derivatives and triazine derivatives as mentioned above, in the presence of p-methylbenzylidenecamphor, are known in Patent Applications DE-100,12,408 and EP-1,046,391.
However, the Applicant Company has found that some of these 1,3,5-triazine derivatives, when they are in the presence of 4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane, are photosensitive, namely: under UV irradiation, they exhibit the disadvantage of chemically decomposing to a significant extent. Under these conditions, the combination of the two screening agents no longer makes possible prolonged broad sun protection of the skin and hair.
In point of fact, following much research carried out in the abovementioned field of photoprotection, the Applicant Company has now discovered that the introduction of a specific amino-substituted 2-hydroxybenzophenone derivative into a composition comprising 4-tert-butyl-4xe2x80x2-methoxy-dibenzoylmethane in combination with at least one 1,3,5-triazine derivative which is photosensitive in the presence of the said dibenzoylmethane makes it possible to improve, in an entirely noteworthy fashion, the photostability of this 1,3,5-triazine derivative within such compositions and therefore the overall effectiveness of these compositions.
This discovery forms the basis of the invention.
A subject-matter of the present invention is thus a cosmetic or dermatological composition for topical use, in particular for the photoprotection of the skin and hair, characterized in that it comprises at least, in a cosmetically acceptable vehicle:
(a) one dibenzoylmethane derivative and
(b) one 1,3,5-triazine derivative which is photosensitive in the presence of a dibenzoylmethane derivative and
(c) one amino-substituted 2-hydroxybenzophenone derivative of formula (VIII) which will be defined later; the said composition not comprising p-methyl-benzylidenecamphor.
Thus, according to the present invention, cosmetic and/or dermatological compositions comprising 4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane in combination with at least one photosensitive 1,3,5-triazine derivative can be prepared, in which compositions the concentration of 1,3,5-triazine derivative remains relatively constant even if these compositions are subjected to the action of light.
Another subject-matter of the present invention is the use of an amino-substituted 2-hydroxybenzophenone derivative of formula (VIII) as will be defined later in the manufacture of cosmetic or dermatological compositions comprising a dibenzoylmethane derivative in combination with at least one photosensitive 1,3,5-triazine derivative for the purpose of improving, in the said compositions, the stability to UV radiation (photostability) of the said 1,3,5-triazine derivative.
Another subject-matter of the present invention is a process for improving the stability to UV radiation (photostability) of a 1,3,5-triazine derivative which is photosensitive in the presence of a dibenzoylmethane derivative; the said process consisting in adding, to the said combination, an effective amount of a 2-hydroxybenzophenone derivative.
The term xe2x80x9ceffective amount of amino-substituted 2-hydroxybenzophenone derivativexe2x80x9d in accordance with the invention is understood to mean an amount sufficient to produce a noteworthy and significant improvement in the photostability of the 1,3,5-triazine derivative in the photoprotective cosmetic composition. This minimum amount of photostabilizing agent to be employed, which can vary according to the nature of the cosmetically acceptable vehicle used for the composition, can be determined without any difficulty by means of a conventional test for measuring photostability.
Other characteristics, aspects and advantages of the present invention will become apparent on reading the detailed description which will follow.
The ratio by weight of the 2-hydroxybenzophenone derivative to the dibenzoylmethane derivative is preferably greater than 1.
A first compound of the compositions according to the invention is thus a 1,3,5-triazinederivative which is photosensitive in the presence of a dibenzoylmethane derivative.
Use may in particular be made, among 1,3,5-triazine derivatives which can be used in the context of the present invention, of those corresponding to the following formula (I): 
in which the A1, A2 and A3 radicals, which are identical or different, are chosen from the groups of formulae (II): 
in which:
Xa, which are identical or different, represent oxygen or the xe2x80x94NHxe2x80x94 radical; xe2x80x94Ra, which are identical or different, are chosen from: hydrogen; an alkali metal; an ammonium radical optionally substituted by one or more alkyl or hydroxyalkyl radicals; a linear or branched C1-C18 alkyl radical; a C5-C12 cycloalkyl radical optionally substituted by one or more C1-C4 alkyl radicals; a polyoxyethylenated radical comprising from 1 to 6 ethylene oxide units and for which the terminal OH group is methylated; and a radical of following formula (III), (IV) or (V): 
in which:
R1 is hydrogen or a methyl radical;
R2 is a C1-C9 alkyl radical;
q is an integer ranging from 0 to 3;
r is an integer ranging from 1 to 10;
A is a C4-C8 alkyl radical or a C5-C8 cycloalkyl radical;
B is chosen from: a linear or branched C1-C8 alkyl radical; a C5-C8 cycloalkyl radical; or an aryl radical optionally substituted by one or more C1-C4 alkyl radicals.
A more particularly preferred first family of 1,3,5-triazine derivatives, disclosed in particular in the document EP-A-0 517 104, is that of the 1,3,5-triazines corresponding to the formula (I) in which the A1, A2 and A3 radicals are of formula (II) and exhibit the following characteristics:
one Xaxe2x80x94Ra represents the xe2x80x94NHxe2x80x94Ra radical with Ra chosen from: a C5-C12 cycloalkyl radical optionally substituted by one or more C1-C4 alkyl radicals; or a radical of formula (III), (IV) or (V) above in which:
B is a C1-C4 alkyl radical;
R2 is the methyl radical;
the other 2 Xaxe2x80x94Ra groups represent the xe2x80x94Oxe2x80x94Ra radical with Ra, which are identical or different, chosen from: hydrogen; an alkali metal; an ammonium radical optionally substituted by one or more alkyl or hydroxyalkyl radicals; a linear or branched C1-C18 alkyl radical; a C5-C12 cycloalkyl radical optionally substituted by one or more C1-C4 alkyl radicals; or a radical of formula (III), (IV) or (V) above in which:
B is a C1-C4 alkyl radical;
R2 is the methyl radical.
A more particularly preferred second family of 1,3,5-triazine derivatives, disclosed in particular in the document EP-A-0 570 838, is that of the 1,3,5-triazines corresponding to the formula (I) in which the A1, A2 and A3 radicals are of formula (II) and exhibit all of the following characteristics:
one or two Xaxe2x80x94Ra groups represent the xe2x80x94NHxe2x80x94Ra radical with Ra chosen from: a linear or branched C1-C18 alkyl radical; a C5-C12 cycloalkyl radical optionally substituted with one or more C1-C4 alkyl radicals; or a radical of formula (III), (IV) or (V) above in which:
B is a C1-C4 alkyl radical;
R2 is the methyl radical;
the other Xaxe2x80x94Ra group or the other two Xaxe2x80x94Ra groups being the xe2x80x94Oxe2x80x94Ra radical with Ra, which are identical or different, chosen from: hydrogen; an alkali metal; an ammonium radical optionally substituted with one or more alkyl or hydroxyalkyl radicals; a linear or branched C1-C18 alkyl radical; a C5-C12 cycloalkyl radical optionally substituted with one or more C1-C4 alkyl radicals; or a radical of formula (III), (IV) or (V) above in which:
B is a C1-C4 alkyl radical;
R2 is the methyl radical.
A particularly preferred 1,3,5-triazine of this second family is 2-[p-(tert-butylamido)anilino]-4,6-bis[p-(2xe2x80x2-ethylhexyl-1xe2x80x2-oxycarbonyl)anilino]-1,3,5-triazine or xe2x80x9cDiethylhexyl Butamido Triazonexe2x80x9d, sold under the trademark xe2x80x9cUvasorb HEBxe2x80x9d by Sigma 3V and corresponding to the following formula: 
in which Rxe2x80x2 denotes a 2-ethylhexyl radical and R denotes a tert-butyl radical.
A preferred third family of compounds which can be used in the context of the present invention, and which is disclosed in particular in the document U.S. Pat. No. 4,724,137, is that of the 1,3,5-triazines corresponding to the formula (I) in which the A1, A2 and A3 radicals are of formula (II) and exhibit the following characteristics:
Xa are identical and represent oxygen;
Ra are identical or different and represent a C6-C12 alkyl radical or a polyoxyethylenated radical comprising from 1 to 6 ethylene oxide units and for which the terminal OH group is methylated.
A particularly preferred 1,3,5-triazine of this third family is 2,4,6-tris[p-(2xe2x80x2-ethylhexyl-1xe2x80x2-oxycarbonyl)anilino]-1,3,5-triazine or xe2x80x9cEthylhexyl Triazonexe2x80x9d, sold in particular under the trademark of xe2x80x9cUvinul T 150xe2x80x9d by BASF and corresponding to the following formula: 
in which Rxe2x80x2 denotes a 2-ethylhexyl radical.
The 1,3,5-triazine derivative or derivatives are generally present in the compositions of the invention at a content which can range from 0.5% to 15%, preferably from 1% to 10%, by weight with respect to the total weight of the composition.
A second compound of the compositions targeted by the present invention is the dibenzoylmethane derivative. As indicated above, the dibenzoylmethane derivatives targeted by the present invention are products already well known per se and disclosed in particular in the documents FR-A-2 326 405, FR-A-2 440 933 and EP-A-0 114 607, the teachings of which documents are, in so far as they affect the actual definition of these products, entirely included by way of references in the present description.
Mention may in particular be made, among dibenzoylmethane derivatives more particularly targeted by the present invention, of, without implied limitation:
2-methyldibenzoylmethane,
4-methyldibenzoylmethane,
4-isopropyldibenzoylmethane,
4-tert-butyldibenzoylmethane,
2,4-dimethyldibenzoylmethane,
2,5-dimethyldibenzoylmethane,
4,4xe2x80x2-diisopropyldibenzoylmethane,
4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane,
2-methyl-5-isopropyl-4xe2x80x2-methoxydibenzoylmethane,
2-methyl-5-tert-butyl-4xe2x80x2-methoxydibenzoylmethane,
2,4-dimethyl-4xe2x80x2-methoxydibenzoylmethane,
2,6-dimethyl-4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane.
Preference is very particularly given, according to the present invention, among the dibenzoylmethane derivatives mentioned above, to the use of 4-tert-butyl-4xe2x80x2-methoxydibenzoylmethane, in particular that offered for sale under the trademark xe2x80x9cParsol 1789xe2x80x9d by Hoffmann-LaRoche, this screening agent corresponding to the following expanded formula (VI): 
Another preferred dibenzoylmethane derivative according to the present invention is 4-isopropyl-dibenzoylmethane, a screening agent sold under the name of xe2x80x9cEusolex 8020xe2x80x9d by Merck and corresponding to the following expanded formula (VII): 
The dibenzoylmethane derivative or derivatives are present in the compositions in accordance with the invention at contents preferably ranging from 0.5 to 15% by weight and more preferably from 1% to 10% by weight with respect to the total weight of the composition.
The amino-substituted 2-hydroxybenzophenone derivatives in accordance with the invention correspond to the following formula (VIII): 
in which:
R1 and R2, which are identical or different, denote a hydrogen atom, a C1-C20 alkyl radical, a C2-C10 alkenyl radical, a C3-C10 cycloalkyl radical or a C3-C10 cycloalkenyl radical;
R1 and R2 can also form, with the nitrogen atom with which they are bonded, a 5- or 6-membered heterocyclic ring member;
R3 and R4, which are identical or different, denote a C1-C20 alkyl radical, a C2-C10 alkenyl radical, a C3-C10 cycloalkyl radical, a C3-C10 cycloalkenyl radical, a C1-C12 alkoxy radical, a (C1-C20)alkoxycarbonyl radical, a C1-C12 alkylamino radical, a di(C1-C12)alkylamino radical, an aryl radical or a heteroaryl which is optionally substituted, or a water-solubilizing substituent chosen from a carboxylate group, a sulphonate group or an ammonium residue;
X denotes a hydrogen atom or a COOR5 or CONR6R7 group;
R5, R6 and R7, which are identical or different, denote a hydrogen atom, a C1-C20 alkyl radical, a C2-C10 alkenyl radical, a C3-C10 cycloalkyl radical, a C3-C10 cycloalkenyl radical, a xe2x80x94(YO)oxe2x80x94Z group or an aryl group;
Y denotes xe2x80x94(CH2)2xe2x80x94, xe2x80x94(CH2)3xe2x80x94, xe2x80x94(CH2)4xe2x80x94 or xe2x80x94CHxe2x80x94(CH3)xe2x80x94CH2xe2x80x94;
Z represents xe2x80x94CH2xe2x80x94CH3, xe2x80x94CH2CH2CH3, xe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94CH3 or xe2x80x94CH(CH3)xe2x80x94CH3;
m is an integer varying from 0 to 3;
n is an integer varying from 0 to 3;
o is an integer varying from 1 to 2.
Mention may be made, as C1-C20 alkyl radicals, of, for example: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethyl-ethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methyl-butyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-icosyl.
Mention may be made, as C2-C10 alkenyl groups, of, for example: vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.
Mention may be made, as C1-C12 alkoxy radicals, of: methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, 1-methylpropoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-methyl-1-ethylpropoxy, octoxy, 2-methylpropoxy, 1,1-dimethylpropoxy, hexoxy, heptoxy or 2-ethylhexoxy.
Mention may be made, as C3-C10 cycloalkyl radicals, of, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclo-propyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclodecyl.
Mention may be made, as C3-C10 cycloalkenyl radicals having one or more double bonds, of: cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, 1,5-cyclooctadienyl, cyclooctatetraenyl, cyclononenyl or cyclodecenyl.
The cycloalkyl or cycloalkenyl radicals can comprise one or more substituents (preferably from 1 to 3) chosen, for example, from halogen, such as chlorine, fluorine or bromine; cyano; nitro; amino; C1-C4 alkylamino; di(C1-C4)alkylamino; C1-C4 alkyl; C1-C4 alkoxy; or hydroxyl. They can also comprise from 1 to 3 heteroatoms, such as sulphur, oxygen or nitrogen, the free valencies of which can be occupied by a hydrogen or a C1-C4 alkyl radical.
The aryl groups are preferably chosen from phenyl or naphthyl rings which can comprise one or more substituents (preferably from 1 to 3) chosen, for example, from halogen, such as chlorine, fluorine or bromine; cyano; nitro; amino; C1-C4 alkylamino; di(C1-C4)alkylamino; C1-C4 alkyl; C1-C4 alkoxy; or hydroxyl. Preference is more particularly given to phenyl, methoxyphenyl and naphthyl.
The heteroaryl groups generally comprise one or more heteroatoms chosen from sulphur, oxygen or nitrogen.
The water-solubilizing groups are, for example, carboxylate or sulphonate groups and more particularly their salts with physiologically acceptable cations, such as alkali metal salts or trialkylammonium salts, such as tri(hydroxyalkyl)-ammonium or 2-methylpropan-1-ol-2-ammonium salts.
Mention may also be made of ammonium groups, such as alkylammoniums, and their salified forms with physiologically acceptable anions. Mention may in particular be made, as examples of the 5- or 6-membered heterocyclic ring member formed by the R1 and R2 radicals with the nitrogen atom, of pyrrolidine or piperidine.
The amino groups can be attached to the benzene ring in the ortho, meta or para position with respect to the carbonyl radical and more preferably in the para position.
A family of preferred compounds of formula (VIII) comprises those chosen from those of following formula (VIIIa): 
in which:
R1 and R2, which are identical or different, denote a hydrogen atom or a C1-C12 alkyl radical or form, with the nitrogen atom with which they are bonded, a 5- or 6-membered heterocyclic ring member;
X denotes COOR5 or CONR6R7;
R5 denotes a hydrogen atom, a C1-C12 alkyl radical or a C3-C6 cycloalkyl radical;
R6 and R7, which are identical or different, denote a hydrogen atom, a C1-C12 alkyl radical or a C5-C6 cycloalkyl radical.
The more particularly preferred compounds of formula (VIIIa) are those for which:
R1 and R2, which are identical or different, denote a C1-C4 alkyl radical and more particularly ethyl;
R5 denotes a C3-C8 alkyl radical;
R6 and R7, which are identical or different, denote a C1-C8 alkyl radical.
Another family of preferred compounds of formula (VIII) comprises those chosen from those of following formula (VIIIb): 
in which:
R1 and R2, which are identical or different, denote a C1-C12 alkyl radical or form, with the nitrogen atom with which they are bonded, a 5- or 6-membered heterocyclic ring member.
Mention may more particularly be made, among the compounds of formula (VIIIb), of:
4-diethylamino-2-hydroxyphenyl phenyl ketone,
4-pyrrolidino-2-hydroxyphenyl phenyl ketone.
A family of more particularly preferred compounds of formula (VIII) comprises those chosen from those of following formula (VIIIc): 
in which:
R1 and R2, which are identical or different, denote a hydrogen atom or a C1-C8 alkyl radical or form, with the nitrogen atom with which they are bonded, a 5- or 6-membered heterocyclic ring member;
R5 denotes a hydrogen atom, a C1-C12 alkyl radical or a C3-C6 cycloalkyl radical.
Mention may be made, among the compounds of formula (VIIIc), of:
2-(4-pyrrolidino-2-hydroxybenzoyl)benzoate
methyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate
2-ethylhexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate
cyclohexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate
[lacuna] 2-(4-dibutylamino-2-hydroxybenzoyl)benzoate
methyl 2-(4-dibutylamino-2-hydroxybenzoyl)benzoate
isobutyl 2-(4-dibutylamino-2-hydroxybenzoyl)benzoate.
A very particularly preferred compound of formula (VIII) is n-hexyl 2-(4-diethylamino-2-hydroxy-benzoyl) benzoate.
The compounds of formula (VIII) as defined above are known per se and their structures and their syntheses are disclosed in Patent Applications EP 1 046 391 and DE 100 12 408 (which form an integral part of the content of the description).
The amino-substituted 2-hydroxybenzophenone derivatives in accordance with the invention are preferably present in the composition of the invention in proportions ranging from 0.1 to 15% by weight and more preferably from 1 to 10% by weight and more particularly from 2 to 8% by weight with respect to the total weight of the composition.
In addition, the compositions in accordance with the invention can comprise other additional organic UV screening agents which are active in the UV-A and/or UV-B regions (absorbers), the said screening agents being water-soluble, fat-soluble or else insoluble in commonly used cosmetic solvents.
The additional organic UV screening agents are chosen in particular from anthranilates; salicylic derivatives; cinnamic derivatives; camphor derivatives, other than p-methylbenzylidenecamphor; benzophenone derivatives, other than those of formula (VIII); xcex2,xcex2-diphenylacrylate derivatives; benzotriazole derivatives; non-photosensitive triazine derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bisbenzoazolyl derivatives as disclosed in Patents EP 669 323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA) derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives as disclosed in Applications U.S. Pat. No. 5,237,071, U.S. Pat. No. 5,166,355, GB 2 303 549, DE 197 26 184 and EP 893 119; screening polymers and screening silicones, such as those disclosed in particular in Application WO 93/04665; dimers derived from xcex1-alkylstyrene, such as those disclosed in Patent Application DE 198 55 649; and 4,4-diarylbutadienes as disclosed in Applications EP 0 967 200, DE 197 46 654, DE 197 55 649 and EP-A-1 008 586.
Mention may be made, as examples of additional organic screening agents which are active in the UV-A and/or UV-B regions, of, denoted below under their INCI names:
Para-Aminobenzoic Acid Derivatives:
PABA,
Ethyl PABA,
Ethyl Dihydroxypropyl PABA,
Ethylhexyl Dimethyl PABA, sold in particular under the name xe2x80x9cEscalol 507xe2x80x9d by ISP,
Glyceryl PABA,
PEG-25 PABA, sold under the name xe2x80x9cUvinul P25xe2x80x9d by BASF,
Salicylic Derivatives:
Homosalate, sold under the name xe2x80x9cEusolex HMSxe2x80x9d by Rona/EM Industries,
Ethylhexyl Salicylate, sold under the name xe2x80x9cNeo Heliopan OSxe2x80x9d by Haarmann and Reimer,
Dipropyleneglycol Salicylate, sold under the name xe2x80x9cDipsalxe2x80x9d by Scher,
TEA Salicylate, sold under the name xe2x80x9cNeo Heliopan TSxe2x80x9d by Haarmann and Reimer,
Cinnamic Derivatives:
Ethylhexyl Methoxycinnamate, sold in particular under the trademark xe2x80x9cParsol MCXxe2x80x9d by Hoffmann-LaRoche,
Isopropyl Methoxy cinnamate,
Isoamyl Methoxy cinnamate, sold under the trademark xe2x80x9cNeo Heliopan E 1000xe2x80x9d by Haarmann and Reimer,
Cinoxate,
DEA Methoxycinnamate,
Diisopropyl Methylcinnamate,
Glyceryl Ethylhexanoate Dimethoxycinnamate,
xcex2,xcex2-Diphenylacrylate Derivatives:
Octocrylene, sold in particular under the trademark xe2x80x9cUvinul N539xe2x80x9d by BASF,
Etocrylene, sold in particular under the trademark xe2x80x9cUvinul N35xe2x80x9d by BASF,
Benzophenone Derivatives:
Benzophenone-1, sold under the trademark xe2x80x9cUvinul 400xe2x80x9d by BASF, 24
Benzophenone-2, sold under the trademark xe2x80x9cUvinul D50xe2x80x9d by BASF,
Benzophenone-3 or Oxybenzone, sold under the trademark xe2x80x9cUvinul M40xe2x80x9d by BASF,
Benzophenone-4, sold under the trademark xe2x80x9cUvinul MS40xe2x80x9d by BASF,
Benzophenone-5,
Benzophenone-6, sold under the trademark xe2x80x9cHelisorb 11xe2x80x9d by Norquay,
Benzophenone-8, sold under the trademarkxe2x80x9cSpectra-Sorb UV-24xe2x80x9d by American Cyanamid,
Benzophenone-9, sold under the trademark xe2x80x9cUvinul DS-49xe2x80x9d by BASF,
Benzophenone-12,
Benzylidenecamphor Derivatives:
3-Benzylidene camphor, manufactured under the name xe2x80x9cMexoryl SDxe2x80x9d by Chimex,
Benzylidene Camphor Sulfonic Acid, manufactured under the name xe2x80x9cMexoryl SLxe2x80x9d by Chimex,
Camphor Benzalkonium Methosulfate, manufactured under the name xe2x80x9cMexoryl SOxe2x80x9d by Chimex,
Terephthalylidene Dicamphor Sulfonic Acid, manufactured under the name xe2x80x9cMexoryl SXxe2x80x9d by Chimex,
Polyacrylamidomethyl Benzylidene Camphor, manufactured under the name xe2x80x9cMexoryl SWxe2x80x9d by Chimex,
Benzimidazole Derivatives:
Phenylbenzimidazole Sulfonic Acid, sold in particular under the trademark xe2x80x9cEusolex 232xe2x80x9d by Merck,
Disodium Phenyl Dibenzimidazole Tetrasulfonate, sold under the trademark xe2x80x9cNeo Heliopan APxe2x80x9d by Haarmann and Reimer,
Triazine derivatives:
Anisotriazine, sold under the trademark xe2x80x9cTinosorbSxe2x80x9d by Ciba Specialty Chemicals,
2,4,6-tris(diisobutyl 4xe2x80x2-aminobenzalmalonate)-s-triazine,
Benzotriazole Derivatives:
Drometrizole Trisiloxane, sold under the name xe2x80x9cSilatrizolexe2x80x9d by Rhodia Chimie,
Methylenebis(benzotriazolyltetramethylbutyl-phenol), sold in the solid form under the trademark xe2x80x9cMixxim BB/100xe2x80x9d by Fairmount Chemical or in the micronized form in aqueous dispersion under the trademark xe2x80x9cTinosorb Mxe2x80x9d by Ciba Specialty Chemicals,
Anthranilic Derivatives:
Menthyl anthranilate, sold under the trademark 25 xe2x80x9cNeo Heliopan MAxe2x80x9d by Haarmann and Reimer, Imidazoline derivatives:
Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,
Benzalmalonate Derivatives:
Polyorganosiloxane comprising a benzalmalonate functional group, sold under the trademark xe2x80x9cParsol SLXxe2x80x9d by Hoffmann-LaRoche,
4.4-diarylbutadiene Derivatives:
1,1-dicarboxy(2,2xe2x80x2-dimxc3xa9thyl-propyl)-4,4-diphxc3xa9nylbutadiene and their mixtures.
The organic UV screening agents which are more particularly preferred are chosen from the following compounds:
Ethylhexyl Salicylate,
Ethylhexyl Methoxycinnamate,
Octocrylene,
Phenylbenzimidazole Sulfonic Acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
4-Methylbenzylidene camphor,
Terephthalylidene Dicamphor Sulfonic Acid,
Disodium Phenyl Dibenzimidazole Tetrasulfonate,
2,4,6-Tris(diisobutyl 4xe2x80x2-aminobenzalmalonate)-s-triazine,
Anisotriazine,
Methylenebis(benzotriazolyltetramethylbutyl-phenol),
Drometrizole Trisiloxane,
1,1-dicarboxy(2,2xe2x80x2-dimethyl-propyl)-4,4- and their mixtures.
The cosmetic compositions according to the invention can also comprise pigments or alternatively nanopigments (mean size of the primary particles: generally between 5 nm and 100 nm, preferably between run and 50 nm) formed from coated or uncoated metal oxides, such as, for example, nanopigments formed from titanium oxide (amorphous or crystallized in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide, which are all UV photoprotective agents well known per se. Conventional coating agents are, furthermore, alumina and/or aluminum stearate. Such coated or uncoated metal oxide nanopigments are disclosed in particular in Patent Applications EP-A-0 518 772 and EP-A-0 518 773.
The compositions according to the invention can also comprise agents for the artificial tanning and/or browning of the skin (self-tanning agents), such as, for example, dihydroxyacetone (DHA).
The compositions of the invention can additionally comprise conventional cosmetic adjuvants chosen in particular from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, agents for combating free radicals, opacifiers, stabilizers, emollients, silicones, xcex1-hydroxy acids, antifoaming agents, moisturizing agents, vitamins, insect repellents, fragrances, preservatives, surfactants, anti-inflammatories, substance P antagonists, fillers, polymers, basifying or acidifying agents, colorants, propellents or any other ingredient commonly used in cosmetics, in particular for the manufacture of antisun compositions in the form of emulsions.
The fatty substances can be composed of an oil or a wax or their mixtures. The term xe2x80x9coilxe2x80x9d is understood to mean a compound which is liquid at ambient temperature. The term xe2x80x9cwaxxe2x80x9d is understood to mean a compound which is solid or substantially solid at ambient temperature and for which the melting point is generally greater than 35xc2x0 C. They also comprise fatty acids, fatty alcohols and esters of fatty acids which are linear or cyclic, such as derivatives of benzoic acid, trimellitic acid and hydroxybenzoic acid.
Mention may be made, as oils, of mineral oils (liquid paraffin); vegetable oils (sweet almond, macadamia, blackcurrant seed or jojoba oil); synthetic oils, such as perhydrosqualene, fatty alcohols, acids or esters (such as the C12-C15 alkyl benzoate sold under the trademark xe2x80x9cFinsolv TNxe2x80x9d by Finetex, octyl palmitate, isopropyl lanolate or triglycerides, including those of capric/caprylic acids), or oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils (cyclomethicone, polydimethylsiloxanes or PDMS); fluorinated oils; or polyalkylenes.
Mention may be made, as waxy compounds, of paraffin wax, carnauba wax, beeswax or hydrogenated castor oil.
Mention may be made, among organic solvents, of lower alcohols and polyols.
Of course, a person skilled in the art will take care to choose this or these optional additional compounds and/or their amounts so that the advantageous properties, in particular the photostability of the triazine derivative, intrinsically attached to the compositions in accordance with the invention are not, or not substantially, detrimentally affected by the envisaged addition or additions.
The compositions of the invention can be prepared according to techniques well known to a person skilled in the art, in particular those intended for the preparation of emulsions of oil-in-water or water-in-oil type.
These compositions can be provided in particular in the form of a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W), such as a cream, a milk, a gel or a cream gel, of a powder or of a solid tube and can optionally be packaged as an aerosol and provided in the form of a foam or spray.
When it is a question of an emulsion, the aqueous phase of the latter can comprise a nonionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
The cosmetic composition of the invention can be used as a composition for protecting the human epidermis or the hair against ultraviolet rays, as an antisun composition or as a make-up product.
When the cosmetic composition according to the invention is used for the protection of the human epidermis against UV rays or as an antisun composition, it can be provided in the form of a suspension or dispersion in solvents or fatty substances, in the form of a nonionic vesicular dispersion or in the form of an emulsion, preferably of oil-in-water type, such as a cream or a milk, in the form of an ointment, gel, cream gel, solid tube, powder, stick, aerosol foam or spray.
When the cosmetic composition according to the invention is used for the protection of the hair against UV rays, it can be provided in the form of a shampoo, lotion, gel, emulsion or nonionic vesicular dispersion and can constitute, for example, a rinse-out composition, to be applied before or after shampooing, before or after dyeing or bleaching, and before, during or after perming or hair straightening, a styling or treating lotion or a styling or treating gel, a lotion or a gel for blow-drying or hair setting, or a composition for perming or straightening, dyeing or bleaching the hair.
When the composition is used as a product for making up the eyelashes, eyebrows or skin, such as a treatment cream for the epidermis, foundation, lipstick tube, eyeshadow, face powder, mascara or eyeliner, it can be provided in the anhydrous or aqueous, pasty or solid form, such as oil-in-water or water-in-oil emulsions, nonionic vesicular dispersions, or suspensions.
By way of indication, for the antisun formulations in accordance with the invention which exhibit a vehicle of oil-in-water emulsion type, the aqueous phase (comprising in particular the hydrophilic screening agents) generally represents from 50 to 95% by weight, preferably from 70 to 90% by weight, with respect to the entire formulation, the oily phase (comprising in particular the lipophilic screening agents) from 5 to 50% by weight, preferably from 10 to 30% by weight, with respect to the entire formulation, and the (co)emulsifier(s) from 0.5 to 20% by weight, preferably from 2 to 10% by weight, with respect to the entire formulation.
As indicated at the beginning of the description, a subject-matter of the invention is the use of a composition as defined above in the manufacture of a cosmetic or dermatological composition intended for the protection of the skin and/or hair against ultraviolet radiation, in particular solar radiation.
Concrete but in no way limiting examples illustrating the invention will now be given.